TW469267B - Photopolymerization initiator and photopolymerizable initiator composition - Google Patents

Abstract

Provided is a photopolymerization initiator which has a high sensitivity and is inexpensive and which does not cause precipitation of crystals when kept in cold storage after diluted and dissolved in an organic solvent. The photopolymerization initiator comprises a structure represented by the following formula (1).

Description

A7 469267 B7__ V. Description of the invention (1) Section of the invention-(Please read the notes on the back before filling out this page) The invention relates to a polymerization initiator, a photopolymerizable initiator composition, and a method for manufacturing Photosensitivity discoloration composition for color liquid crystal display parts and color filters of color solid-state image development and playback parts. BACKGROUND OF THE INVENTION A polymerization method in which when a monomer or oligomer system having a polymerizable unsaturated group such as a vinyl group polymerizes to harden a coating film, applying light in the presence of a photopolymerization initiator has the advantage that it hardens Speed is faster than other methods and can harden at low temperatures, so it is widely used in coatings and photoresist. The hardening speed depends on the photopolymerization initiator, so different photopolymerization initiators have been released so far. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, German Patent 1,694,149, for example, phenyl ether. In addition, photo-radical generators such as propylene-based diazonium salts and halogenated hydrocarbons are known. Furthermore, it is known that specific organic peroxides are used for the polymerization initiator, and many investigations have been made on this polymerization system. In particular, aromatic compounds having a designated tert-butyl peroxide are disclosed in U.S. Patents 4,171,252, 4,416,826 and 4,752,649. Furthermore, the synthesis of benzophenone derivatives with one or two peroxy acid esters, for example, in the Journal of Organic Chemistry, vol. 4, page 4 1 2 3 (19 7 9) and the Journal of Polymer Chemistry In Vol. 21, p. 3129 (1983), the polymerization of 4,4-bis (t-butylperoxycarbonyl) benzophenone and vinyl monomers has been studied. This paper is compliant with Chinese National Standard (CNS) / U specifications (210 X 297 mm> -4- A7 469267 B7 V. Description of the invention (2) However, among these compounds, those who have a peroxy acid ester Those who had this defect had low photopolymerization activity, and those who had two peroxoesters had this defect. After diluting and dissolving in organic solvents, their crystals tend to precipitate during refrigeration and their raw materials are expensive and expensive to manufacture. A benzophenone derivative with four peroxy acid esters, published in Japanese Patent Publication No. 60322/1991, has good photopolymerization activity and is not expensive in terms of raw materials, but it has this defect and its crystals are diluted After being dissolved in an organic solvent, it precipitates during refrigerating. Furthermore, the peroxy acid ester published in Japanese Patent Laid-Open Publication No. 1 7 5 4 7/1 9 9 8 has a high level when refrigerated after being diluted and dissolved in an organic solvent. The sensitivity is not precipitated into crystals. In any case, it is defective, in which the manufacturing process is long and involves difficult reactions, which results in high manufacturing costs. Total inventions As described in detail above, one of the objects of the present invention is to provide a photopolymerization initiator which has high sensitivity and is not expensive, and wherein precipitation of crystals does not occur when it is diluted and dissolved in an organic solvent and refrigerated. Another object is to provide a photopolymerizable initiator composition using the photopolymerization initiator, a photosensitive dyeing composition, and a color filter. That is, the first direction of the present invention is the following chemical formula ( 1) Photopolymerization initiator indicated: (Please read the precautions on the back before filling out this page) Packed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the consumer co-operative society The paper size is applicable to China National Standard (CNS) A4 (210 X 297) Mm> -5- 6 9267 A7 _____B7 V. Description of the invention (3) 〇 0

Among them, 1 and 2 respectively represent a tertiary alkyl group containing 4 to 15 carbon atoms or a tertiary aralkyl group containing 9 to 15 carbon atoms; and 1 and X2 each represent _0— Or —NH-; R3 represents an organic group containing 1 to 30 carbon atoms in which an atom bonded to Xi is not an oxygen atom; and R4 represents an organic group containing 1 to 30 carbon atoms An organic group in which one of the atoms bonded to X2 is not an oxygen atom, a tertiary alkoxy group containing 4 to 15 carbon atoms, or a tertiary aryloxy group containing 9 to 15 carbon atoms. An example of a preferred system is one in which —X i _ R 3 and _X2-R4 in chemical formula (1) each represent an alkoxy group, which is a methanol, ethanol, 2-propanol, 1_butanol, or benzyl alcohol. An example of an alcohol fragment, each of which represents one. Alkoxy is a 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and poly (meth) acrylate A fragment or example of an alcohol of ethylene glycol, polypropylene glycol mono (meth) acrylate or hydroxybutyl (meth) acrylate, each of which represents an alkoxy group and which is a dimethylaminoethanol or diethylamino group Fragments of ethanol. The second direction of the present invention is a photopolymerization initiator represented by the following chemical formula (2): The degree of fork of this paper applies the Chinese national standard (CNSM4 specification (210x297 mm)) < Please read the precautions on the back first (Fill in this page again) Binding 11 --- I —— II 丨 -Institute of Consumer Cooperatives of Intellectual Property Bureau of the Ministry of Economic Affairs -6- 4 6 9 2 6 7 A7 B7 V. Description of Invention (4

COO-Rn R

Where R R 7

R The Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs printed a tertiary courtyard with 4 to 15 carbon atoms or a tertiary aralkyl group with 9 to 15 carbon atoms; only 6 and 12 each represent one A tertiary alkoxy group containing 4 to 15 carbon atoms' a tertiary aralkoxy group containing 9 to 15 carbon atoms or an organic group containing 1 to 30 carbon atoms The atom bound to χ3 is not an oxygen atom: χ3 represents a 10- or _NH_; Rl3 represents an alkenyl group containing 2 to 8 carbon atoms: m represents an integer from 1 to 3 0; and 11 represents a 0 to An integer of 0. An example of a preferred system is one of X3-R6 and one-r12 in chemical formula (2). Each represents an alkoxy group, which is a methanol, ethanol, 2-propanol, 1-butanol or benzyl alcohol. An example of an alcohol fragment, each of which represents an alkoxy group, which is a 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and polyethylene glycol (meth) acrylate. Ester, or a fragment of an alcohol of poly (meth) acrylate or hydroxybutyl (meth) acrylate or an example in which each of them represents an alkoxy group—a dimethylaminoethanol or = ethylaminoethanol Fragment of alcohol. The third direction of the present invention is a photopolymerizable initiator composition containing more than one type of photopolymerization initiator represented by chemical formula (1) or (2). The paper & degree applies the Chinese National Standard (CNS > A4 specification) (210 X 297 public meals) ί Please read the notes on the back of the page before filling in this page) Pack --- !! Order ---! — -Green Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs d 0 9 2 6 7. A? ____ B7_____ V. Description of the invention (5) Hair spray. -The fourth direction of the present invention is the photopolymerization initiator composition described above, in which one or more photopolymerization initiators other than those represented by the chemical formulae (1) and (2) and / or one or more The sensitizing dye is based on the total weight of the photopolymerization initiator or the sensitizing dye and is used in an amount of 1 to 80% (all percentages thereafter represent weight%). The preferred amount is 10 to 70%. The fifth aspect of the present invention is a photosensitive dyeing composition composed of a photopolymerizable initiator composition of the third invention incorporated with a color material. The sixth aspect of the present invention is by using the above-mentioned photosensitive A color filter made of a dyeing composition. A seventh aspect of the present invention is a liquid crystal display part made by using the above color filter. Brief Description of the Figures Figure 1 is a proton NMR chart of a compound obtained by oxidizing 3,3 ', 4,4 * -benzophenone tetracarboxylic dianhydride and chlorinating the carboxylic acid. Detailed description of the invention The compound represented by the chemical formula (1) according to the present invention can be obtained by containing a benzophenone structure, for example, 3,3 >, 4,4 --- benzophenone tetracarboxylic dianhydride The reaction of tetracarboxylic dianhydride with primary alcohol, secondary alcohol or phenol in the presence of tertiary amines such as pyridine or triethylamine to form a paper containing carboxyl groups. Applicable to the National Solid State Standard (CNS) A4. (210 X 297 mm)

-Q (Please read the precautions on the back before filling out this page) Loading --- I order.! 1. · 469267 π Β7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Description of the invention (6) Amidamine compounds or carboxyl-containing ester compounds, using thionyl chloride, phosphorus pentachloride or phosgene to compound the results The carboxyl group in the carboxylic acid is converted into carboxylic chloride, which is then reacted with a peroxy alcohol in the presence of a basic compound such as sodium hydroxide, triethylamine or pyridine. Primary amines used in the present invention 1 Primary alcohols, secondary alcohols and phenols include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine 'sec'-butylamine, tert-butylamine, 1- (2-amino Ethyl) 2-pyrrolidone, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 1-hexanol, 2-hexane Alcohol, cyclohexanol, 2-ethylhexanol, octanol, dodecanol, stearyl alcohol, 1- (2-hydroxyethyl) -2-pyrrolidone, 3-cyclohexene_1-methanol, phenol , 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene poly (meth) acrylate, (meth) Hydroxybutyl acrylate, furfuryl alcohol, tetrahydrofurfuryl alcohol, compounds derived from tetrahydrofurfuryl alcohol modified with ε-caprolactone, benzyl alcohol, dimethylaminoethanol, and diethylaminoethanol. From the viewpoint of manufacturing cost, methanol, ethanol, 2-propanol, 1-butanol, and benzene. Methanol are particularly preferable because they are not expensive. From the viewpoint of the sensitivity of the photopolymerization initiator, especially the 2-hydroxyethyl (meth) acrylate, the polyethylene glycol (meth) acrylate, the polypropylene (meth) acrylate, and ( Because hydroxybutyl methacrylate is closely related to the (meth) acrylic hydroxyl group, as a result, the compound has an improvement effect as a polymerization initiator. Furthermore, when dimethylaminoethanol or diethylaminoethanol is used, the sensitivity will be enhanced by the influence of ammonia. · From the display of the photopolymerization initiator composition (please read the precautions on the back before filling in this page) Installation • ti ---- order -------- I --- beginning, this paper is applicable National Standard (CNS) A4 specification (210 x 297 mm) -9- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4,1 ^ 46 92 6 7 A7 ____B7 V. Description of the invention (7) Tetrahydrofurfuryl alcohol and compounds derived from tetrahydrofurfuryl alcohol modified with ε-caprolactone are particularly preferred because the pattern formed by development is good. In this example, 'includes a hydroxyl-containing compound formed by the addition reaction of ε-caprolactone with hydrogen contained in an alcohol and a compound formed by the addition reaction of the same compound to caprolactone. However, in R3 or R4, the number of carbon atoms is limited to 30. Peroxyalcohols that react with acid chloride include tert-butanol, tert-peroxide, t-hexanol, t-octanol, and cumene. From the viewpoint of manufacturing cost, tert-peroxide is particularly preferred. According to the present invention, the compound represented by the chemical formula (2) can be obtained by having a benzophenone structure, for example, 3,3-, 4,4 -_benzophenone tetracarboxylic dianhydride, tetracarboxylic acid di Anhydride is present with ethylene glycol, ethylene glycol, polyethylene glycol * propylene glycol, propylene glycol 'polypropylene glycol, 1,4-butanediol, ethylenediamine or hexamethylenediamine in a tertiary amine such as pyridine or triethylamine The next reaction is followed by the compound of formula (1) to produce carboxy chloride in the same way and further react it with peroxy alcohol. Furthermore, 'R_5, R7, Rs, R9, Rio, and Rii have the same meanings as R \ and R2 in Chemical Formula (1). R 6 and R i 2 have the same meaning as ruler 3 and ruler 4 in Chemical Formula (1), and the same raw materials can be used to make the repeated compound. The compound represented by the chemical formula (2) has high sensitivity because it has many peroxy acid ester structures in the molecule. In addition, the physical properties of the hardened coating film can be controlled by adjusting the length of the alkane chain, so it is very useful. Glycerol or triethanolamine can be reacted with the above-mentioned acid anhydride. In this case, this paper is again applicable to the Chinese Standards (CNS) A ·} specification (210x 297 mm > ------ ^ ------ ', installed ----- order- ----— |! Start-{Please read the precautions on the back before filling out this page) -10- 469267 A7 ______B7____ 5. In the description of the invention (8), the molar ratio is carefully controlled "If the molecular weight becomes extremely high , Processing may become difficult. _ < Read the precautions on the back before filling this page) The photopolymerization initiator of the present invention thus obtained is not expensive in terms of manufacturing cost and has high sensitivity. The precipitation of crystals does not occur during refrigeration after being diluted and dissolved in the solvent. It has excellent characteristics as a component of a photopolymerizable initiator composition. _ The photopolymerizable initiator composition can be obtained by blending and dissolving the photopolymerization initiator, photopolymerizable monomer, and solvent of the present invention. Β The photopolymerization initiator of the present invention, when used alone, the i-beam and h-beam And g beam has low sensitivity. Therefore, when these beams are used, the photopolymerization initiator should be used in combination with other photopolymerization initiators and / or sensitizing dyes. The Ministry of Economic Affairs, the Ministry of Economic Affairs, the Consumer Cooperatives, and other designated examples of printing photopolymerization initiators or sensitizing dyes include benzophenone, Michler, ketones, 4,4-_bis (diethylamino) benzophenone, 〇 Methyl ketone, thioxanthone, 2,4-diethyl thioxanthone, 2-ethylanthraquinone, phenylmethyl ketone, 2-hydroxy-2-methylpropyl ketone, 1 Monohydroxycyclohexylphenyl_, isopropylphenyl ether, isobutylphenyl ether, 2,2-diethoxy.ylphenylmethyl ketone, 2,2-dimethoxy-2-phenyl Phenylmethyl ketone, biphenyl hydrazone, camphor quinone, benzoxanthone, 2-methyl-1- [4- (methylthio) phenyl] -2—morinyl-propanone-1_one, Benzyl_2-dimethylamino-1-1 (4-morpholinyl) monobutanone_1, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isoamyl ester, 4 , 4 ^ -bis (tert-butylperoxycarbonyl) benzophenone, 3, 4,4 < -tri (tert-butylperoxycarbonyl) benzophenone, 3,3 <, 4, 4, tetrakis (tert Butylperoxycarbonyl) benzophenone '2, 4, 6 — three papers are again applicable to China National Standard (CNS) A4 specifications ( 210x297 mm) -11-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 469267 A7 ___B7 V. Description of the invention (9) Methylphenylfluorenyl-diphenylphosphine oxide, -2,4,6-trishenylbenzene Fluorenyl-phenylphosphinic acid methyl ester, 2,4-dichlorophenylphosphonium monoxide, 2,6-dichlorophenylphosphonium-phosphine oxide, 2,3,5,6-tetramethylbenzene -Diphenylphosphine oxide, 3,4-dimethylphenylfluorenyl-diphenylphosphine oxide, bis (2,4,6-trimethylphenylfluorenyl) monophenylphosphine oxide, bis (2, 6-Dimethoxyphenylfluorenyl) _2,4,4-trimethylmonophenylphosphine oxide, 4-a [p-N, N-bis (ethoxycarbonylfluorenylmethyl)]-2,6- Bis (trichloromethyl) _symmetric monotriazabenzene, 1, 3 —bis (trichloromethyl)] _ 5 ~ · (2 < —chlorophenyl) —symmetric monotriazabenzene, 1, 3 _Bis (trichloromethyl)]-5-(4 < -chlorophenyl) -symmetric mono-triazabenzene, 2- (p-dimethylaminostyryl) benzoxazole, 2-(p- —Dimethylaminostyryl) benzothiazole and 3,3′-carbonylfluorenylbisdiethylamine humorin). It is also effective to use them as a mixture of two or more of them. Among the above, the preferred ones are 4,4-bis (diethylamino) benzophenone, 2-methyl_1_ [4_ (methylthio) phenyl] -1 2-morpholinylpropane-1- Ketones and 2-benzyl-2-dimethylamino-1— (4-morpholinyl) monobutanone-1 = especially in this case, among which 4, 4 bis (diethylamino) benzophenone And 2-benzyl-1, 2-dimethylamino-1, 1- (4-morpholinyl) -butanone-1, or in this example, 4, 4 # —bis (diethylamino) benzyl Ketone, 2-benzyl-1, 2-dimethylamino-1 — (monomorpholinyl) monobutanone 1 and 2-methyl-1 1 [4- (methylthio) phenyl] -2 —Morpholine-propane-one-one ketones are used * because of sensitivity | Compatibility with resins and storage Anben paper size applies to Chinese national standards (CNSM4 specification (210 * 297 mm) < Please read the back first Please note this page before filling in this page) · Order III · I II — 5. -12- 46 9 2 6 A7 B7 Ministry of Economic Affairs. € · Institute of Property Bureau Employee Consumption Cooperative ¾ 5. Description of invention (10) High qualitative and The patterned edges are equally good. The blending ratio of the photopolymerization initiator and the sensitizing dye in the photopolymerizable initiator composition of the present invention is based on the total amount of the adhesive polymer and the photopolymerizable monomer, and the total of the polymerization initiator and the sensitizing dye is The amount should be 2 to 10 ◦%. If it is less than 2%, the actual sensitivity may not be obtained, and if it exceeds 100%, the sensitivity reaches the highest limit, then ‘cost will increase. Adhesive polymers suitable for use in the photocurable initiator composition of the present invention include, but are not limited to, (meth) acrylic resin, polyester, polyimide, polystyrene, epoxy resin, benzene Ethylene-maleic anhydride copolymer, butyral resin, polyvinyl alcohol, polyamide, phenol resin, polyurethane, cellulose-based polymer, polyvinylpyrrolidone, polyethylene glycol, polymer Propylene glycol, polyethyleneimine, melamine resin, guanamine, polyethylene and polypropylene. In recent years, the demand for a polyfunctional photopolymerizable initiator composition that can remove an unexposed portion using an alkaline solution to form a predetermined pattern has increased. Suitable for this purpose are (meth) acrylic resin, styrene-maleic anhydride copolymer, polyvinyl alcohol, phenol resin polyvinylpyrrolidone, polyethylene glycol and polypropylene glycol. Particularly suitable are (meth) acrylic resins and styrene-maleic anhydride copolymers, which are easy to control using the alkaline development characteristics. The blending ratio of the binder polymer is preferably 1 to 70% of the total amount of the photopolymerization initiator composition, but it may not be in this range. For example, the binder polymer 1 is not used depending on the application. The photopolymerizable monomer used in the photopolymerizable initiator of the present invention includes * (Please read the precautions on the back before filling this page)

---- Order --- I 5. The paper & degree applies to the Chinese national standard (CNSM4 specification (210 * 297 mm) -13- A7 A7 469267 B7__ V. Description of the invention (11) (谙 read the first Please fill out this page again) Printed by the Intellectual Property Bureau of the Ministry of Economy, but not limited to this, monofunctional monomers · such as (meth) acrylic acid, (meth) acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, ( (Meth) n-butyl dienoate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, 2 ~ ethylhexyl (meth) acrylate, hexyl (meth) acrylate, ( Cyclohexyl methacrylate, octyl (meth) acrylate * tridecyl (meth) acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic acid Benzyl methyl ester, 2-methoxyethyl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, (methyl ) 3-methoxybutyl acrylate, phenoxyethyl (meth) acrylate, cetyl (meth) acrylate, isoamyl (meth) acrylate, dimethylamine (meth) acrylate Tetravalent product of ethyl ethyl ester, dimethylamino ethyl (meth) acrylate, morpholinyl ethyl (meth) acrylate, trimethylsilyl ethyl (meth) acrylate, Biscoat # 193, Biscoat # 320, Biscoat # 231HP 'Biscoat # 220, Biscoat # 2000' Biscoat # 2100 'Biscoat # 2150' Biscoat # 2180 'Biscoat 3F v Biscoat 4F' Biscoat 4FM 'Biscoat 6FM' Biscoat 8F, Biscoat 8FM, Biscoat 17F, Biscoat 17FM And Biscoat MTG, each of which is manufactured by Osaka Organic Chemical Co., Ltd., M-101, M-102, M-110, M-1 13, Ml 17 'M-1'2 0' M-5300 'M -5600, M-5700, T〇—850, TO-851, TO-1248, TO-1249, TO—1301, TO- This paper has a common Chinese National Standard (CNS) A4 specification (210 X 297 mm) -14- A7 469267 B7__ V. Description of the invention (12) 1317'ΤΟ-1315'-Τ 0-981 'TO-1215, TO-1316, TO-13 22, TO-1 342, TO-1 3 40 and ΤΟ-1 225, each of which is manufactured by Toa Gosei Co., Ltd., cyclohexene-3,4-dicarboxylic acid (2-((meth) acryloxy) ethyl), (meth) acrylic acid-3 —Cyclohexenyl methyl ester, 2- (meth) acrylic acid 2-tetrahydrobenzylidene ethyl ester, (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, N, N-dimethylacrylamide, styrene, α-methylstyrene, maleic anhydride, N-vinylpyrrolidone and 4-propenyl morpholine, and polyfunctional monomers such as trimethylpropanetri (trimethyl) ) Acrylic acid, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acrylic acid phosphate Ethyl ethoxylate, polyethylene di (meth) acrylate, ethylene oxide isotricyanate modified tri (meth) acrylic acid, ethylene isotrimeric acid modified di (meth) acrylic acid, polyacetic acid ( Methacrylic acid and diglycerol tetra (meth) acrylate. It is certain that two or more of the monomers may be used in a mixture. Among these monomers, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are suitable because of their high sensitivity. In particular, dipentaerythritol pentaerythritol and dipentaerythritol hexaacrylate are in The coating film surface is preferred because it has good anti-spatter properties after being hardened by photopolymerization. The non-exposed part of the application of the polyfunctional photopolymerizable initiator composition can be removed with an alkaline solution to obtain a predetermined pattern, and a single paper can be blended and used in accordance with the national standard (CNS) A4 specification ( 210 X 297 public love) 11II111111 ί. — — — — — — I— «— — 111111 (Please read the precautions on the back before filling out this page) Employee Cooperation of the Ministry of Economic Affairs, Smart Time and Industry Bureau 钍 印 钍 -15- A7 469267 ______B7___ 5. Description of the invention (13) Examples of functional monomers and difunctional monomers_such as polyethylene diacrylate, polypropylene diacrylate, ethylene phthalate, and KAYARD TC-1 1 OS 'KAYRAD R-712' KAYRAD R-551 and KAYRAD R-684 * Each type is manufactured by Nippon Kayaku Co., Ltd. The blending ratio of β photopolymerizable monomers effective for controlling the formation of pattern edges is not affected by It is particularly limited and based on the total amount of the photopolymerizable initiator composition, usually 1 to 90%. The solvent used for the photocurable initiator composition of the present invention is not particularly limited as long as it dissolves the photopolymerization initiator, the adhesive monomer, and the photopolymerizable monomer, and can be used, for example, water, ethanol, 2-propanol, 2-butanol, ethyl acetate, butyl acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethyl diethylene glycol monoethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate , Ethylene glycol monobutyl ether acetic acid, cyclohexanone 'cyclopentanone, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, toluene, xylene, γ-butanone and Ν, Ν-dimethyl Acetamide. Among these solvents, based on the uniformity of the coating film thickness, propylene glycol-ether, propylene glycol monomethyl ether acetic acid, cyclohexanone, and toluene are more preferable. It is certain that two or more of them can be mixed. The formation of a non-solvent type photopolymerizable initiator composition using β without a solvent is suitable from the viewpoint of environmental impact. Adding a silane coupling agent, a leveling agent, a surfactant, an additive, and the like to the photopolymerizable initiator composition of the present invention is effective for enhancing different characteristics of the composition. Blending of the dyeing material and the photopolymerizable initiator composition can be used to make a photosensitive dyeing composition. The meaning of this paper applies to the Chinese National Standard (CNS) A4 specification (210 * 297 mm) .1. ---------- Loading · -------- Order ·! ---! Han (谙Read the notice on the back before filling out this page) Seal of Consumer Cooperation of Employees of the Intellectual Property Bureau of the Ministry of Economy 4 |, take * 16- ^ 6 9267 A7 B7 V. Description of the invention (14) The specified examples of the dyeing material include synthetic dyes such as Azo dyes, anthraquinone dyes, triphenylmethane dyes, polymethan dyes, metal complex salt dyes, diazo dyes, trisazo dyes, sulfur-containing dyes, indigo dyes, and organic pigments such as C. I. Pigment Yellow 12, 13, 14, 17, 20, 24, 31, 55, 83'93, 109, 110, 137, 139, 150, 153, 154, 166, 168 and 173 'C, I. Pigment Orange 36, 43 and 51, C. I. Pigment Red 9, 97, 122, 123, 149, 176, 177, 180, 215 and 254, C. I. Pigment Violet 19, 23 and 29, C. I. Pigment Blue 15, 15: 3 and 15: 6, CI Pigment Blacks 1 and 7. The use of the photosensitive dyeing composition in color filters is increasing year by year. In view of heat resistance and light fastness, organic pigments are preferred. From the viewpoint of color purity and penetration, C.I. Pigment Red 17 7 and 254, C · I. Pigment Yellow 139 and 150, CI Pigment Green 36 and C · I. Pigment Blue 15 and 15: 6, especially good. The blending properties of these dyeing materials will not be particularly limited and based on the total amount of the photosensitive dyeing composition, it is usually 1 to 50%. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs f Please read the notice on the back before filling out this page} 5, Examples The present invention will be further explained below with reference to examples. Example 1 50 grams of 3 ′ 3-, 4,4 benzophenone tetra-residic acid dianhydride, 25 grams of pyridine, 20 grams of methanol, and 1000 grams of toluene are mixed and the Chinese national standard is applied to this paper again ( CMS) A4 specification (210x297 mm) 469267 A7 B7 V. Description of invention (15) (谞 Please read the notes on the back before filling in this page) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs at 80 ° C. 1 〇 hour. The excess methanol was distilled off, and then .60 g of thionyl chloride was added at 30 ×: it was slowly added dropwise. After the dropwise addition was complete, the solution was stirred at 30 ° C for 1 hour, further heated to 50 ° C, and stirred for 2 hours. After the reaction was completed, unreacted thionyl chloride and toluene were removed under reduced pressure to obtain crude acid chloride. The residue was dissolved again in toluene and washed once with water, and then the organic layer was separated. After this was dried over anhydrous sodium sulfate, the desiccant was filtered off, and the final solution was concentrated under reduced pressure to give a pale yellow viscous acid chloride. The proton N M R spectrum of this compound is shown in FIG. 1 using tetramethylsilane as a reference material. According to this map, it is obvious that the intensity ratio of the absorption peak of the hydrogen atom of the benzene ring at about 8 p pm to the absorption peak of the hydrogen atom of methyl at about 4 p pm is 6.000 / 6.135 = 6/6. This is the desired compound. The absorption peak near 7.5 ppm and the absorption peak at 3 ppm are absorption peaks based on the reaction solvent toluene. Next, 100 g of a 10% toluene solution of tert-peroxide in peroxy and 10 g of triethylamine were mixed and cooled ', and the toluene solution of the above acid chloride was slowly added dropwise to complete the dehydrochlorination reaction. After the completion of the dropwise addition, the solution was stirred at 5 ° C for 1 hour and then at room temperature for 3 hours. After removing triethylamine by filtration, the solution was washed twice with water and dried over anhydrous sodium sulfate. Then, toluene was distilled off under reduced pressure to obtain 42 g of a 25% toluene solution of a photopolymerization initiator having a structure shown below. The concentration of the photopolymerization initiator is determined from the loss on drying. This example may include tert-peroxybutyl and methoxy groups connected to four carbonyl groups which are connected to 3_, 3 > —, 4 a and 4 — a position at 3-position and 4-position and 3 / -Position and 4 *-Papers between each other are applicable to China Gujia Standard (CNS) A4 (210x297 mm) -18 · 8 9 2 6 7 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau, Ministry of Economic Affairs ^ ^ V. Description of the Invention (16) Replacement. 0 0 0

A 25% toluene solution of this photopolymerization initiator was stored at 5 ° C for 3 months, but no crystalline precipitate was observed. Comparative Example 1 3,3 <, 4,4 >-A solution of 2% 5% toluene in tetra (t-butylperoxycarbonyl) benzophenone was stored at 5 ° C for 3 months, and precipitation of crystals was observed . Example 2 50 g of 3,3 >, 4,4 < monobenzophenone tetracarboxylic dianhydride, 25 g of pyridine., 9 g of ethylene glycol and 100 g of toluene-based mixture and mixed at 80 ° C The reaction took 10 hours. The solution was cooled to 30 ° C, and then 60 grams of thionyl chloride was slowly added dropwise at 30 eC. After the dropwise addition was completed, the solution was stirred at 30 ° C for 1 hour, further heated to 50 ° C and stirred for 2 hours. After the reaction was completed, unreacted thionyl chloride and toluene were removed under reduced pressure to obtain crude acid chloride. The residue was dissolved again in toluene and washed once with water, and then the organic layer was separated. After drying on anhydrous sodium sulfate, 'the desiccant was filtered off, and the paper was concentrated under reduced pressure, and the Chinese solid standard (CNS) A4 specification (210 X 297 mm >) was used. — — — III — — — — ! ri ------ II ---- 11 (Please read the notes on the back before filling out this page) 0 92 6 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of Invention (17) The final solution was obtained as a pale yellow viscous acid chloride. This was a 2 5% toluene solution of a photopolymerization initiator of the chemical formula (2) obtained by reacting with tert-peroxide in the same manner as in Example 1. This was stored in 3 months at 5 ° C, but no sinking of crystallization was observed. Examples 3 to 9 The photopolymerization initiators were synthesized with the same reagents and the same mole ratios as those used in Example 1, except for those used in Example 1. Methanol is changed to ethanol, n-butylamine, 1-butanol, benzyl alcohol, 2-hydroxyethyl acrylate, hydroxybutyl acrylate, and tetrahydrofurfuryl alcohol. The 25% toluene solution of these photopolymerization initiators is stored in the system. 3 months at 5 t, but no precipitation of crystals was observed. Example 10 Photoinitiator It was synthesized with the same reagents and the same molar ratios as in Example 1, except that the tert-peroxide used in Example 1 was changed to per-t-hexanol. 2 of these photopolymerization initiators The% toluene solution was stored at 5 ° C for 3 months, but no precipitation of crystals was observed. Example 1 1 0. 50 g of benzyl methacrylate / methyl methacrylate / acrylic acid-2-hydroxyethyl Ester / methacrylic acid tetravalent copolymer (Molar ratio 46: 16: 13: _25, weight average molecular weight: 7,000 which is measured by GPC using polyethylene oxide as a reference), 2. 00 g Polypropylene glycol—ether acetate, 0.40 g by Toa Gosei This paper is sized to the Chinese National Standard (CNS) A4 (210 * 297 mm) ----------- Λ.pack —! I Order _! (Please read the note § on the back before filling this page) A7 469267 _B7____ V. Description of the invention (18) Co., Ltd. M — 4 0 0, 0. 10 grams of M made by Toa Gosei Co., Ltd. — 240, 0.05 g of 4,4-bis (diethylamino) benzophenone, 0.20 g of the photopolymerization initiator synthesized in Example 1, 2 5% of methylbenzyl alcohol, and 0.0 0 2 g of B YK_ 3 0 0 series manufactured by Bic Chemie Japan Co., Ltd. was mixed and then stirred to obtain a photopolymerizable initiator composition. The photopolymerizable initiator composition was spin-coated on a glass substrate at 12 rpm. It was left on for 5 seconds and dried on a hot plate at 90 ° C. for 1 minute, wherein the thickness of the film was 1 to 36 μm. This substrate was exposed in the air through a mask with a pattern of 20 μm thin strips at a gap of 100 μm to a U I-5 0 1 C ultrahigh-pressure mercury lamp manufactured by Ushio Co., Ltd. After exposure, the glass substrate was rinsed and developed in a developing solution in which 5 g of sodium bicarbonate and 2.5 g of sodium carbonate were dissolved in 5000 g of demineralized water to remove the unexposed portion, and the final patterned film Thickness measurement = The exposure energy in which the film thickness is infiltrated is 15 mj, where the film thickness is 1.3 1 μm. Example 1 2. The photopolymerization initiator synthesized in Example 2 was manufactured in the same manner as in Example 11 to produce a photopolymerizable initiator composition. The film thickness before the exposure is 1.4 μm, and the exposure energy in which the film thickness is penetrated is 1 om j * wherein the film thickness is 1.3 6 μm. Example 1 3 5 grams of Solspars manufactured by Zeneca Co., Ltd. are dissolved in 20 grams of C. (Please read the notes on the back before filling out this page)-II! Order · ί I! I * Completed by the Intellectual Property Office of the Ministry of Economic Affairs Consumption cooperatives printed off agricultural paper again applied the Chinese National Standard (CNS) A4 specification (210x297 mm) -21-Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 9 2 6 7 A7 __B7 __ V. Description of the invention ( 19) Glycol monomethyl ether acetic acid, and 1-2 g of C.I. Pigment Red 254 and 3 g of C.I. Pigment Yellow 1 39 were added thereto. The mixture was kneaded by a three-roll mill, and then 60 g of propylene glycol monomethyl ether acetic acid and 400 g of zirconia particles having an outer diameter of 0.5 mm were added, followed by stirring for 20 hours by a sand mill. . This solution was filtered through a Teflon membrane filter having a pore size of 1 to obtain 95 g of a red dispersion. The entire photopolymerizable initiator composition prepared in Example 12 was slowly added dropwise to 2 g of the red dispersion while stirring to obtain a red photosensitive dyeing composition. This was evaluated in the same manner as in Example 11. The film thickness before the exposure was 1.2 μm, and the exposure energy in which the film thickness was penetrated was 25 mj, where the film thickness was 1.2 3 μm. The final pattern was post-baked at 200 ° C for 10 minutes and then heated at 250 ° C for 1 hour. Observing the color change, it was found that ΔE was 0.31 and the heat resistance was good. Comparative Example 2 3, 3, 4, 4, Tetra (tert-butylperoxycarbonyl) benzophenone A 25% toluene solution was used in the same manner as in Example 11 to produce a photopolymerizable initiator composition. In addition, the photosensitive dyeing composition was manufactured and evaluated in the same manner as in Example 13. The film thickness before exposure was 1 · 28 μm, and the exposure energy in which the film thickness was infiltrated was 45 mj, where the film thickness was 1.21 μm »ΔE system 0.30 'and the heat resistance was good. According to the present invention, an inexpensive, high-sensitivity and high-quality paper can be obtained. Applicable to the Chinese standard (CNS) A4 grid (210 X 297 cm) -22-

------------ ^^ -------- Order -------- Complete {Please read the notes on the back before filling this page J Intellectual Property Bureau of the Ministry of Economy Printed by the employee consumer cooperative 4 6 9 Z 6T A7 _ B7 _______- V. Description of the invention (2Q) Photopolymerization initiator for storage stability. -A photopolymerizable initiator composition using the photopolymerization initiator has high sensitivity. Furthermore, by further mixing the dyeing material, for example, a pigment having the same high sensitivity and high heat resistance can be obtained to obtain a photosensitive dyeing composition and will exhibit the same excellent characteristics as a color filter material. National Standard (CNS) A4 Specification (210x297 mm) (Please read the precautions on the back before filling this page) Loading -------- Order ί ------- 气 -23-

Claims (1)

469267 Profit range A8 BS C8 D8 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 • ~ Photopolymerization Initiator > It is represented by the following chemical formula. (1) * 0 j | 0 η Ri-OOC, II ^ 2,000-¾ I (1) R3—II, iso-x2-r4 0 II 0 where R 1 and R; each: do not represent a secondary courtyard containing 4 to 15 carbon atoms or one Tertiary aralkyl groups containing 9 to 15 carbon atoms; X: 1 and X 2 each represent--0 or one N Η one; R 3 represents--an organic group containing-L to 30 carbon atoms One of the atoms in the group bonded to X i is not an oxygen atom: R 4 represents an organic group in which the organic group contains 1 to 30 carbon atoms and one of them is bonded to: Atom is a tertiary alkoxy group containing 4 to 15 carbon atoms or a tertiary aralkoxy group containing 9 to 15 carbon atoms. 2. If the photopolymerization initiator in item 1 of the scope of the patent application, wherein the chemical formula (1). Chinese — XI — R 3 and —X 2 — R 4 each represent — — a group of oxygen, which is a methanol, ethanol, 2 Fragments of monopropanol, 1-butanol or benzyl alcohol. 3. The photopolymerization initiator according to item 1 of the patent application range, wherein —X 1 —R 3 and —X 2 —R 4 in the chemical formula (1) each represent an alkoxy group, which is a (meth) acrylic acid— 2-hydroxyethyl ester, (meth) acrylic acid 2-hydroxypropyl vinegar, mono (meth) acrylic acid polyethylene glycol --- (meth) acrylic acid polypropylene vinegar or hydroxybutyl (meth) acrylate Fragment of alcohol (please read the notes on the back before filling this page) This paper size applies to China National Standard (CNS) A4 (210X297 mm) -24-Α8 BS C8 D8 469267 6. Application for Patent Consumption 4. For example, the photopolymerization_initiator of the first patent application scope, wherein one of the chemical formula (1) X — Ra and one X2_R4 each represents an alkoxy It is a fragment of an alcohol of dimethylaminoethanol or diethylaminoethanol. 5. The photopolymerization initiator according to item 1 of the scope of patent application, wherein one of the formulas (X) — R3 and — R4 each represents an alkoxy group, which is a tetrahydrofurfuryl alcohol, and tetrahydrofurfuryl alcohol is added to ε- Caprolactone gives fragments of monohydric alcohols. .6 · A photopolymerization initiator, which is represented by the following chemical formula (2) {please «please note f on the back before filling in the text of this text） COO-R "X 疒 r12-Order. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs, among which Rs, R7, Re, R9 'Ri. And R. " Representatives-each containing 4 to 15 carbon atoms A tertiary compound or a tertiary aralkyl group containing 9 to 15 carbon atoms; 6 and & 12 each represent a secondary compound oxygen group containing 4 to 15 carbon atoms, and one containing 9 to Tertiary aralkoxy group of 15 carbon atoms or an organic group containing 1 to 30 carbon atoms in which one atom bonded to X3 is not an oxygen atom; χ3 represents or -NΗ-; Ru represents one containing Alkenyl groups of 2 to 8 carbon atoms; m represents an integer from 1 to 30; and η represents an integer from 0 to 30. This paper is based on the Chinese National Standard (CNS) A4. ≪ 210X297 mm) -25- 6 2 9 6 4 888 8 ABCD VI. Application scope of patents (please read the note f on the back before filling this page) 7 · If you apply for the photopolymerization initiator of scope 6. Among them, —X3—R6 and X3 ~ R12 in chemical formula (2) each represent an alkoxy group, which is a methanol, ethanol, 2-propanol, 1-butanol, or benzyl. Fragments of alcohols. 8. The photopolymerization initiator according to item 6 of the scope of patent application, wherein one of the chemical formula (2) X3 — Re and one X3 — Ri2 each represents an alkoxy group which is a (methyl ) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene poly (meth) acrylate or hydroxybutyl (meth) acrylate Fragments of alcohols of esters. 9. The photopolymerization initiator of item 6 of the patent application, wherein one of the chemical formula (2) X3-R6 and one X3-Rl2 each represents an alkoxy group which is a dimethylamine Fragment of alcohol based on diethanolamine or diethylaminoethanol 0 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 1 〇 If the photopolymerization initiator in the scope of the patent application No. 6, where _X3_Re and 1 in the chemical formula (2) χ3 —: [^ 12 each represents an alkoxy group which is a fragment of a monohydric alcohol obtained by adding ε-caprolactone to tetrahydrofurfuryl alcohol and tetrahydrofurfuryl alcohol. 1 1. A photopolymerizable initiator composition, It contains more than one type represented by Chemical Formula (1) or (2) Polymerization initiator 1 2. The photopolymerizable initiator composition according to item 11 of the patent application scope, wherein one or more photopolymerization initiators other than those represented by chemical formulae (1) and (2) and / or A sensitizing dye is based on the total weight of the photopolymerization initiator or sensitizing dye, and the weight is 1 to 80. This paper is applicable in the national standard ® CNS) A4 gauge (210X297 mm) -26- 469267 A8 B8 D8 VI. Amount of patent application%. -. 1 3.-A photosensitive dyeing composition, which is composed of a photopolymerizable initiator composition incorporated in a color material in the scope of application for item 11 of the patent. 1 4. A color filter made by using a photosensitive dyeing composition according to item 13 of the patent application scope. 1 ··· A kind of liquid crystal display part, which is made by using a color filter in the scope of claim 14 of the patent application. (Please read the note on the back before reading this page before filling out this page) Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs, Printed by the Consumer Cooperatives of the Ministry of Economic Affairs This paper uses China's national rubbing rate (CNS > A4 size (210X2D7mm))-• 27-